Method for the synthesis of para‐aramid nanofibers

The synthesis and electrospinning of novel N‐substituted aramid nanofibers (ANFs) prepared from basic dispersions of commercial microscale Kevlar fibers are herein reported. The functionalized ANFs were characterized via Fourier transform infrared spectroscopy, ¹³C solid‐state nuclear magnetic resonance spectroscopy, and X‐ray diffraction to confirm proper N‐substitution of the side groups and to determine changes to the polymer crystallinity and stability. These analyses suggested that the electrospun ANFs consisted of numerous crystalline domains in the transverse fiber direction with large amorphous regions that were void of defects commonly found in commercial Kevlar fibers. A semi‐empirical study of the variations in the solubility parameter due to various side chain moieties was conducted to facilitate solvent selection and to elucidate the enhanced solubility effects with selected organic solvents. These initial findings suggest a promising route for obtaining a new class of nanofibers with ultrahigh strength and stiffness. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44082.     

Specific heavy metal ion recovery with ion‐imprinted cryogels

In this study, the functional monomers, N‐methacryloyl‐l ‐aspartic acid and N‐methacryloyl‐l ‐cysteine were synthesized through a reaction between appropriate amino acids and methacryloyl chloride. Then, Pb(II) or Cd(II) ion‐imprinted 2‐hydroxyethyl methacrylate based cryogels were prepared by free radical polymerization method under partially frozen conditions. Following the characterization of matrices, adsorption of heavy metal ions was examined in batch mode from aqueous solution considering several parameters affecting the adsorption performance. The actual adsorption capacities were 44.5, 65.3, and 86.7 mg/g for Cd‐1, Cd‐2, and Cd‐3 cryogels meanwhile those were 41.9, 86.3, and 122.7 mg/g for Pb‐1, Pb‐2, and Pb‐3 cryogels, respectively at optimum pH: 5.5. By increasing temperature, adsorption capabilities of both cryogels were inhibited because of the electrostatic nature of coordinated covalent bonds and collapsing of coordination spheres. The adsorption process was very fast, the equilibrium adsorption was achieved in about 60 min, which was directly related to macroporous structure and interconnected flow‐channels of cryogels. Kinetics and adsorption isotherms were also studied. Langmuir isotherms and pseudo‐second order kinetic model were well suited to adsorption data, which also indicated that the process occurred without any diffusion restrictions or steric hindrances. Finally, the competitive adsorption studies were performed using multi‐ion containing synthetic wastewater to show whether the cryogels developed are suitable for specific heavy metal recycling or not. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43095.     

Flocculation behavior of cationic pea starch prepared by the graft copolymerization of acrylamide for wastewater treatment

To improve the flocculation efficiency of coal mine wastewater treatment, we synthesized a cationic flocculant by grafting acrylamide (AM) onto pea starch, and we performed the characterization with elemental analysis, Fourier transform infrared spectrometry, scanning electron microscopy, thermogravimetric analysis, and NMR. The effects of the synthesis conditions were also investigated, and the optimal synthesis parameters of the cationic flocculant were obtained. The mass ratio between pea starch and AM was 0.5 with a reaction temperature of 65 °C. The dosages of ceric ammonium nitrate and 3‐chloro‐2‐hydroxypropyl‐trimethylammonium chloride were 0.02 and 0.11 mol/L, respectively. Application experiments for wastewater treatment were carried out consequently, and the optimal dosage of cationic pea starch was 40 mg/L within the pH range 6–8. Compared with other traditional flocculation products, the cationic pea starch showed the best flocculation behavior for coal mine wastewater. Therefore, the cationic pea‐starch‐grafted AM may be applicable as a novel flocculant in wastewater treatment and has already demonstrated outstanding features. It is bound to replace other traditional flocculants in the future. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43922.     

Liquid‐phase catalytic thermal cleavage of thiocarbonylthio end‐groups for polymers synthesized by RAFT polymerization: Influences of different solvents

Catalytic thermal cleavage of thiocarbonylthio end‐groups for RAFT synthesized polymers is usually accompanied by other side reactions such as chain‐scission and crosslinking. Occurrence of these side reactions depends on polymers, end‐groups, and oxidation–reduction property of reaction media in a liquid phase. Herein, well‐defined hydrophilic poly(4‐vinylpridine) (P4VP) and hydrophobic polystyrene (PS) are synthesized via a controlled RAFT polymerization in the presence of S‐1‐Dodecyl‐S′‐(R,R′‐dimethyl‐R″‐acetic acid) trithiocarbonates (DDMAT). Then their thiocarbonylthio end‐groups are cleaved through catalytic thermolysis in a liquid phase. Under the catalysis of Cu(0), all S‐containing groups can be removed at 165 °C in 3 h. To study the effect of solvent on thermolysis and microstructure of polymer, nitrobenzene of oxidation property and diethylene glycol of reduction property are chosen as solvents. Because of oxidizing property of nitrobenzene, Z groups of RAFT agent are eliminated at the same time that thiocarbonylthio end‐groups are removed. Therefore crosslinking among multipolymer chains occurs. While diethylene glycol is used as a solvent, no crosslinking occurs. Diethylene glycol is superior to nitrobenzene for synthesis of well‐defined polymer without S‐containing groups. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43992.     

Montmorillonite as support for peroxide in the melt grafting of maleic anhydride onto polypropylene

Grafting of maleic anhydride onto polypropylene was performed in a Haake torque rheometer, in the presence of organically modified montmorillonite, MMT (used as support for the peroxide), according to a 2³ factorial design, where the maleic anhydride concentration (C_MA), peroxide concentration (C_per) and reaction time (t_r) were varied. For comparison, the reaction in the absence of MMT was also conducted. Polypropylene degradation was assessed by parallel plate rheometry and size exclusion chromatography (SEC) and percentage of reacted maleic anhydride (%MA_g) was obtained by titration and FTIR spectroscopy. The results showed differences in both systems, conventional and in the presence of MMT. The structure of polypropylene grafted with maleic anhydride, PP‐g‐MA, indicates longer branches are formed in the presence of MMT compared to in its absence, demonstrated by FTIR analysis. As in conventional reaction systems, an increase in C_per caused an increase in %MA_g and a reduction in molar mass. The variable C_MA showed to be not significant in the grafting reaction in the presence of MMT, even at high DCP levels, at a 5% significance level. On the other hand, increase in C_MA resulted in significant increase in viscosity. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44134.     

Molecular dynamics simulations of molecularly imprinted polymer approaches to the preparation of selective materials to remove norfloxacin

A novel molecularly imprinted polymer (MIP) designed by molecular dynamics (MD) simulations was successfully prepared with norfloxacin as a template molecule, methyl acrylic acid as a functional monomer, and ethylene glycol dimethacrylate as a crosslinker. According to the theoretical prediction and experimental preparation methods, three kinds of molecular imprinting materials were designed and synthesized with MD simulations and molecular imprinting technology. The best ratio of the template to the functional monomer to the crosslinker was 1:8:40 in these studies. The experimental results illustrate that the MD simulations were credible in compounding the components of the MIPs. The structure of the prepared polymers were characterized with various methods. To analyze the adsorption performances, many kinds of static adsorption tests, including kinetic, isotherm, and selectivity tests, were used. The results indicate that the novel adsorbents conformed to the pseudo–second‐order kinetic equation and followed the Langmuir isotherm model. The adsorption amounts of MIP2 at a ratio of 1:8:40 were about 29.35 mg/g at 298 K_. The selective adsorption and reusable performance of norfloxacin were excellent. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 132, 42817.     

烯烃复分解法制备端基官能化液体橡胶研究进展

用烯烃复分解法制备端基官能化液体橡胶具有分子量可控、易于引入多种官能团、反应条件较温和等优势。本文即综述了利用烯烃复分解法制备端羟基、端羧基、端酯基等官能化液体橡胶的研究新进展,并提示了其今后的发展方向。     

The solution behavior of hydrophobically associating zwitterionic polymer in salt water

The acrylamide‐based hydrophobically associating zwitterionic polymer was prepared, which was composed of dimethyl‐dodecyl‐allyl ammonium chloride as hydrophobic group and carboxyl betaine 2‐(4‐acrylamido‐propyl‐dimethyl ammonic)‐sodium acetate as functional group. Hydrophobically associating polyacrylamide (HAPAM) was also prepared for comparative study. The behaviors of polymers in pure water and salt solutions were investigated by the means of apparent viscosity test, laser light scattering, atomic force microscope, and fluorescence experiments. The viscosities of polymer solution increased with the increasing of salt concentration, which indicated that the addition of salt resulted in significant antipolyelectrolyte effect in the zwitterionic polymer solution. The results of dynamic laser light scattering experiment also showed that the average hydrodynamic diameters of the zwitterionic polymer molecules increased with the increasing of salt concentration. The network structures had been observed by atomic force microscope and the addition of salt strengthened the formation of network structures. The results of fluorescence experiment showed that the addition of salt could enhance the association of hyrophobically zwitterionic polymer. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39707.     

PMMA composites of single‐walled carbon nanotubes‐graft‐PMMA

To facilitate the dispersion of single‐walled carbon nanotubes (SWCNT) into poly(methyl methacrylate) (PMMA), SWCNT were functionalized with a RAFT chain transfer agent, and PMMA was grafted from the SWCNT by reversible addition–fragmentation transfer (RAFT) polymerization to give SWCNT‐g‐PMMA containing 6 wt % PMMA. SWCNT‐g‐PMMA in the form of small bundles was dispersed into PMMA matrices. The SWCNT‐g‐PMMA filler increased the glass transition temperature (T_g) of the composite when the matrix molecular weight M_n was less than the graft molecular weight, but not when the matrix M_n was equal to or greater than the graft M_n. The threshold of electrical conductivity of the composites as a function of weight percent SWCNT increased from 0.2% when matrix M_n was less than graft M_n to about 1% when matrix M_n was greater than graft M_n. Dynamic mechanical analyses of the composites having graft M_n less than or equal to matrix M_n showed broader rubbery plateaus with increased SWCNT content but no significant differences between samples with different grafted PMMAs. The results indicate that lower M_n matrix wets the SWCNT‐g‐PMMA whereas higher M_n matrix does not wet the SWCNT‐g‐PMMA. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39884.     

Strength improvements in toughened epoxy composites using surface treated GnPs

Nanographitic materials are gaining enormous interest as a new class of reinforcement for nanocomposites, promising revolutionary electrical, thermal, and mechanical properties. However, the progress has been quite limited especially in terms of mechanical properties. Here we report a significant leap, >2× increases in tensile strength and modulus of an epoxy composite using surface treated graphite nanoplatelets (GnPs). This corroborated by increases in Tgs as well as the presence of oxygen‐functionalized groups verified by XPS, suggest improved distribution and chemical interaction at the filler‐to‐matrix interface. Toughness values also showed increases with concentration, without compromising the strength or failure strain. However, if solvent levels during degassing were not reduced sufficiently, negligible contributions to strength and stiffness were observed with GnP loading. Subsequent elevated temperature treatments increased the strength of the composite due to cure enhancement of the matrix material, yet did not provide mechanical enhancements due to the incorporation of the filler. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40802.